KR20190092514A - Photo Lewis Acid Generator - Google Patents

Abstract

Unlike conventional photoacid generators, compounds that can generate Lewis acids by light are provided. The compound is composed of an anion moiety containing boron as a center atom and a specific cation moiety (eg, cation whose gap between HOMO-LUMO is 5.3 eV or less). The cation moiety may have a skeleton selected from, for example, an N-substituted pyridinium skeleton, an N-substituted bipyridinium skeleton, an N-substituted quinolinium skeleton, and a pyryllium skeleton.

Description

Photo Lewis Acid Generator

The present invention relates to a compound capable of generating Lewis acid by light irradiation (light energy) and a composition containing the compound.

An acid generator is a compound which produces | generates a protonic acid (brasted acid) by light or heat, and is used for a polymerization initiator, a chemically amplified resist, etc. (refer patent documents 1-3).

Japanese Laid-Open Patent Publication No. 2014-205624 Japanese Unexamined Patent Publication No. 2014-214129 Japanese Laid-Open Patent Publication 2001-183821

An object of the present invention is to provide a compound capable of generating Lewis acid by light, an optical Lewis acid generator composed of the compound, and a composition containing these compounds or agents.

The conventional photoacid generators, components generating a protonic acid by light or heat in the cation moiety, and no piggyback on SbF ₆ ^- or BF ₄ ^-, etc. of the inorganic _{anion, (C 6 F 5) 4} B - , etc. Although organic anions are used, there is a need to improve such that they can be used only in systems to which protonic acid can be applied, and toxic metals such as antimony need to be used in the anion portion.

In the meantime, the present inventors earnestly examined from the viewpoint of not being able to obtain a compound capable of generating Lewis acid by light, unlike the conventional concept of a photoacid generator. And by combining a specific cation moiety, a compound capable of generating Lewis acid from the anion moiety (photo Lewis acid generator) is obtained, and the acid generated from such a compound is a Lewis acid having a different reactivity from protonic acid, They found that boron is the central atom, and is generally a strong Lewis acid and a high value for use.

In addition to the above, the present inventors have obtained various new findings as described below, and have intensively studied to complete the present invention.

That is, the compound of the present invention is a compound having a boron as a center atom and a cation moiety (a salt of a cation moiety and an anion moiety), which is a Lewis acid (in detail, boron as the center) from the anion moiety by light irradiation. Lewis acid as an atom).

Such a compound of the present invention is, in particular, an anion moiety having an aryl group containing boron as a center atom and containing at least one halogen atom, and a cation moiety, which can generate Lewis acid from the anion moiety by light irradiation. The compound which exists may be sufficient.

The compound (photo Lewis acid generator) of this invention can generate Lewis acid by light. Therefore, it can be applied to various uses (for example, a photoinitiator (photo latent polymerization initiator), chemically amplified resist, etc.) which can use a Lewis acid.

Moreover, since the compound of this invention comprises the center atom of the anion part from boron, and does not need to contain a metal like antimony, it is excellent also in safety and it is very useful.

[compound]

The compound of this invention has an anion part and a cation part which have boron as a center atom. And this anion part can generate | occur | produce Lewis acid (Lewis acid which has a boron as a center atom) by light irradiation.

(No part)

Anion part will not be specifically limited if boron is a center atom and can generate Lewis acid by light. The group (or atom) substituted (or bonded) to the boron atom (> B <) [or boron anion (> B <) ^- ] which is the center atom of the anion part is not specifically limited, For example, a hydrocarbon group And heterocyclic groups (such as heteroaryl groups), hydroxyl groups, halogen atoms and hydrogen atoms.

As the hydrocarbon group, for example, an aliphatic hydrocarbon group [for example, an alkyl group (for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, C _1-20 alkyl groups such as n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, preferably C _2-10 alkyl, more preferably C _2-6 Alkyl group), cycloalkyl group (e.g., C _3-20 cycloalkyl group such as cyclopentyl group, cyclohexyl group, preferably C _4-8 cycloalkyl group), aralkyl group (e.g., benzyl group, phenethyl group, etc.) C _6-10 aryl C _1-4 alkyl group)], aromatic hydrocarbon group [for example, an aryl group (e.g., a C _6-20 aryl group such as a phenyl group, tolyl group, xylyl group, naphthyl group), preferably Preferably a C _6-12 aryl group, more preferably a C _6-10 aryl group).

The hydrocarbon group and the heterocyclic group may have a substituent. In addition, the hydrocarbon group which has a substituent means the group in which 1 or 2 or more of the hydrogen atoms which comprise the hydrocarbon group which do not have a substituent are substituted by the substituent, and the heterocyclic group which has a substituent means the hydrogen atom which comprises the heterocyclic ring which does not have a substituent. 1 or 2 or more substituted with the substituent. The substituent may be further substituted with a substituent.

It does not specifically limit as a substituent, For example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a hydroxyl group, an alkoxy group (for example, a methoxy group, an ethoxy group) C _1-20 alkoxy groups such as, preferably C _1-10 alkoxy groups, more preferably C _1-4 alkoxy groups), aryloxy groups (eg, C _6-10 aryloxy groups such as phenoxy groups) ), Acyl groups (for example, C _1-10 alkylcarbonyl groups such as acetyl groups; C _6-10 arylcarbonyl groups such as benzoyl groups, etc.), acyloxy groups (for example, C _1-10 such as acetoxy groups) Alkylcarbonyloxy group; C _6-10 arylcarbonyloxy group such as phenylcarbonyloxy group), alkoxycarbonyl group (for example, C _1-10 alkoxycarbonyl group such as methoxycarbonyl group), aryloxycarbonyl group (example For example, a C _6-10 aryloxycarbonyl group such as a phenoxycarbonyl group, a mercapto group, an alkylthio group (for example, C _1-20 alkylthio group such as methylthio group, preferably C _1-10 alkylthio group, more preferably C _1-4 alkylthio group), arylthio group (for example, phenylthio group, etc.) C _6-10 arylthio group), amino group, substituted amino group (e.g., mono or di C _1-4 alkylamino group such as dimethylamino group), amide group (e.g., N, N'-dimethylaminocarbonyl group, etc.) Mono or di C _1-4 alkylaminocarbonyl group), cyano group, nitro group, substituted sulfonyl group (for example, arylsulfonyl group such as C _1-10 alkylsulfonyl group such as mesyl group, C _6-10 tosyl group) And hydrocarbon groups (for example, hydrocarbon groups exemplified above such as alkyl groups).

These substituents may be used individually or as a combination of 2 or more types, and a hydrocarbon group or a heterocyclic group may contain 1 or 2 or more substituents.

These substituents may be couple | bonded directly to the boron atom individually or using 2 or more types.

In a preferred embodiment, the anion moiety may have at least one aryl group (aryl group bonded to a boron atom, aryl boron skeleton), and in particular, at least one aryl group (fluoroaryl group) having at least one halogen atom. You may have a dog.

As the halogen atom, chlorine and fluorine are preferable, and fluorine is more preferable.

Especially, it is more preferable to have at least 1 aryl group which has at least 3 halogen atoms, and it is still more preferable to have at least 1 aryl group which has at least 5 halogen atoms. If it is the said aspect, there exists a tendency for Lewis acid strength to increase and the characteristic as a polymerization initiator will improve.

In the aryl group which has a halogen atom, a halogen atom may be couple | bonded with the aryl group directly, or may have in the aspect which a halogen atom containing group couple | bonds with an aryl group, and may have it in the aspect which combines them.

As a halogen atom containing group, For example, a halogen containing hydrocarbon group [For example, haloalkyl group (For example, halo, such as a trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, a perfluorooctyl group, etc.). C _1-20 alkyl group, preferably fluoro C _1-10 alkyl group, more preferably C _1-4 fluoroalkyl group, usually perfluoroalkyl group, halocycloalkyl group (for example, perfluorocyclopropyl group) , A halo C _3-20 cycloalkyl group such as a perfluorocyclobutyl group, a perfluorocyclopentyl group, a perfluorocyclohexyl group, preferably a fluoro C _4-8 cycloalkyl group, usually a perfluorocycloalkyl group) Haloalkoxy groups (e.g., halo C _1-20 alkoxy groups such as trifluoromethoxy group, pentafluoroethoxy group, heptafluoropropoxy group, perfluorooctoxy, preferably fluoro C _1-10 alkoxy group, more Preferably, a C _1-4 fluoroalkoxy group, usually a perfluoroalkoxy group), a halogenated sulfanyl group (for example, a pentafluorosulfanyl group (-SF ₅ ), etc.), etc. may be mentioned.

As an aryl group which has a specific halogen atom (especially a fluorine atom), it is a fluoroaryl group [For example, a pentafluorophenyl group, 2-fluorophenyl group, 2,3- difluorophenyl group, 2,4] -Difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 3,5-difluorophenyl group, 2,3,6-trifluorophenyl group, 2,4,6- Trifluorophenyl group, 2,3,4,6-tetrafluorophenyl group, 2,3,5,6-tetrafluorophenyl group, 2,2 ', 3,3', 4,4 ', 5,5' , 6-nonnafluoro-1,1'-biphenyl group, preferably pentafluorophenyl group, 2,6-difluorophenyl group, 2,4,6-trifluorophenyl group, 2,3,5,6 -Tetrafluorophenyl group, 2,2 ', 3,3', 4,4 ', 5,5', 6-nonafluoro-1,1'-biphenyl group, etc.], (fluoroalkyl) aryl group [ For example, 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 2-pentafluoroethylphenyl group, 3-pentafluoroethylphenyl group, 4- Tafluoroethylphenyl group, 2,4-bis (trifluoromethyl) phenyl group, 2,5-bis (trifluoromethyl) phenyl group, 2,6-bis (trifluoromethyl) phenyl group, 3,5-bis (Trifluoromethyl) phenyl group, 2,4,6-tris (trifluoromethyl) phenyl group, 2,4,6-trimethylphenyl group, preferably 2,6-bis (trifluoromethyl) phenyl group, 3, 5-bis (trifluoromethyl) phenyl group, 2,4,6-tris (trifluoromethyl) phenyl group, etc.], fluoro- (fluoroalkyl) aryl group [for example, fluoro-trifluoromethylphenyl Group (-C ₆ H ₃ FCF ₃ ), fluoro-bis (trifluoromethyl) phenyl group (-C ₆ H ₂ F (CF ₃ ) ₂ ), fluoro-pentafluoroethylphenyl group (-C ₆ H ₃ Fluoro- (fluoro C _1-20 alkyl) C _6-10 such as FCF ₃ CF ₂ ) and fluoro-bis (pentafluoroethyl) phenyl group (-C ₆ H ₂ F (CF ₃ CF ₂ ) ₂ ) aryl group, preferably fluoro - (C _1-10 fluoroalkyl) C _6-10 aryl groups, more preferably Fluoro-by (C _1-4 fluoro-alkyl) group, typically fluoro-perfluoro-alkyl aryl group or the like], an aryl group, chloro e.g., pentachlorophenyl group, a 2-chlorophenyl group, a 2,3-dichlorophenyl group , 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 3,5-dichlorophenyl group, 2,3,6-trichlorophenyl group, 2,4,6-trichlorophenyl group, 2 , 3,4,6-tetrachlorophenyl group, 2,3,5,6-tetrachlorophenyl group, preferably pentachlorophenyl group, 2,6-dichlorophenyl group, 2,4,6-trichlorophenyl group, etc.], ( Fluorosulfanyl) aryl groups [For example, 2-pentafluorosulfanylphenyl group, 3-pentafluorosulfanylphenyl group, 4-pentafluorosulfanylphenyl group, 2, 4-bis (pentafluorosulfanyl ) Phenyl group, 2,5-bis (pentafluorosulfanyl) phenyl group, 2,6-bis (pentafluorosulfanyl) phenyl group, 3,5-bis (pentafluorosulfanyl) phenyl group, 2,4,6 -Tris (pentafluorosulfanyl) phenyl group, 2 , 4,6-trimethylphenyl group, preferably 2,6-bis (pentafluorosulfanyl) phenyl group, 3,5-bis (pentafluorosulfanyl) phenyl group, 2,4,6-tris (pentafluoro Sulfanyl) phenyl group etc.] etc. are mentioned.

Among these, in particular, pentafluorophenyl group, 2,6-difluorophenyl group, 2,4,6-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group, 2,2 ', 3, 3 ', 4,4', 5,5 ', 6-nonafluoro-1,1'-biphenyl group, pentachlorophenyl group, 2,6-dichlorophenyl group, 2,4,6-trichlorophenyl group, 2- Trifluoromethylphenyl group, 2,6-bis (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4,6-tris (trifluoromethyl) phenyl group, etc. are preferable. .

When the anion part has an aryl group (aryl group bonded to a boron atom), the number of aryl groups should just be 4 (a valence of boron anion) or less, Preferably it is 1-4, More preferably, it is 2-3, Especially preferably, it is 3.

In particular, when the anion part has an aryl group (an aryl group bonded to a boron atom) having a halogen atom (especially a fluorine atom), the number of aryl groups having a halogen atom is 1 to 3, preferably 2 to 3, particularly preferred. To be three.

The anion moiety (borate anion) is preferably represented by the following formula (1).

[Formula 1]

(In the formula, Ar ¹ , Ar ² and Ar ³ are an aryl group which may have the same or different substituents, and R ¹ represents a substituent.)

In said Formula (1), in Ar <^1> , Ar <^2> and Ar < ³ (an aryl group which may have a substituent), the aryl group and substituent which were illustrated above are mentioned as an aryl group and a substituent.

In a preferred embodiment, at least one of Ar ¹ , Ar ² and Ar ³ (preferably 2 or 3, more preferably 3) has an aryl group having at least one halogen atom [groups exemplified above For example, a fluorophenyl group, a chlorophenyl group, a (fluoroalkyl) phenyl group, a fluoro- (fluoroalkyl) phenyl group, etc.] etc. are mentioned.

Especially, it is more preferable that at least 2 of Ar <^1> , Ar <^2> and Ar <^3> is an aryl group which has at least 1 halogen atom, and it is more preferable that ³ of Ar <^1> , Ar <^2> and Ar <3> are aryl groups which have at least 1 halogen atom. More preferred. If it is the said aspect, there exists a tendency for Lewis acid strength to increase and the characteristic as a polymerization initiator will improve.

In addition, Ar <^1> , Ar <^2> and Ar <^3> may be the same and may differ. For example, when Ar ¹ , Ar ^2, and Ar ³ are all aryl groups having fluorine atoms, they may all be aryl groups (eg, pentafluorophenyl groups, etc.) having the same number of fluorine atoms, and different numbers of The combination of the aryl group which has a fluorine atom may be sufficient.

Moreover, in said Formula (1), the substituent illustrated above is mentioned as R <^1> (substituent). As a typical substituent, a hydrocarbon group, a heterocyclic group, a hydroxyl group, etc. are mentioned.

As preferable R <^1> , the hydrocarbon group or hydroxyl group which may have a substituent is mentioned, The hydrocarbon group which may have a substituent especially is preferable. If it is the said aspect, it exists in the tendency for a Lewis acid to generate | occur | produce more efficiently.

In the hydrocarbon group which may have a substituent, the group illustrated above is mentioned as a substituent and a hydrocarbon group.

Representative R ¹ includes an alkyl group (for example, a C _1-20 alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, preferably a C _1-10 alkyl group, more preferably a C _2-6 alkyl group), and an aralkyl group. (For example, a C _6-10 aryl C _1-4 alkyl group such as a benzyl group, a phenethyl group), an aryl group (for example, a C _6-10 aryl group such as a phenyl group, a tolyl group), and the like. , R ¹ is preferably an aliphatic hydrocarbon group such as an alkyl group or an aralkyl group.

Moreover, the compound of this invention can generate Lewis acid from an anion part by light irradiation. Such Lewis acid is a compound in which one substituent is detached from four substituents (four substituents bonded with boron as a central atom) bonded to boron, although the aspect of the anion part or the like is normal.

For example, when an anion part is an anion part of Formula (1), the compound in which any one group of Ar <^1> , Ar <^2> , Ar <^3> and R <^1> detach | releases is generated as Lewis acid.

In particular, when R ¹ is desorbed, a compound represented by the following formula (for example, tris (pentafluorophenyl) borane (a compound in which Ar ¹ , Ar ² and Ar ³ are all pentafluorophenyl groups)) is Lewis. Occurs as an acid.

[Formula 2]

(Wherein Ar ¹ , Ar ² and Ar ³ are the same as above)

In particular, the compound of the present invention can generate Lewis acid derived from an anion moiety using boron as a center atom by light irradiation, but by selecting such an anion moiety, a strong Lewis acid [eg, tris ( Fluoroaryl boranes such as pentafluorophenyl) borane] may be generated.

In addition, inorganic anions such as SbF ₆ ^- and BF ₄ ^- generate corrosive HF gas, and the (C ₆ F ₅ ) ₄ B ^- used as the organic anion becomes colored or decomposed when the temperature becomes high. However, in this invention, generation | occurrence | production of such HF gas and coloring and decomposition of resin can be suppressed.

(Cateon part)

The cation moiety is not particularly limited as long as the cation moiety is a counter cation of the anion moiety and can generate Lewis acid from the anion moiety in combination with the anion moiety.

In particular, as described above, the generation of Lewis acid often involves charge transfer from anion to cation by irradiation with light and desorption of substituents.

Therefore, it is preferable that the charge (electron) transfer from an anion part becomes easy in order for a cation part to detach | desorb a substituent (accelerate | desorption of a substituent) quickly from an anion part.

From this point of view, the cation portion has a relatively low gap (energy difference) between HOMO-LUMO, for example, 5.5 eV or less (for example, 5.3 eV or less), preferably 5.2 eV or less (for example, , 5.1 eV or less), more preferably 5 eV or less (for example, 4.5 eV or less), and more preferably 4.2 cV or less.

In addition, although the minimum of a gap is not specifically limited, For example, 1 eV, 1.5 eV, 2 eV, etc. may be sufficient.

The cation moiety is preferably non-reactive with the Lewis acid (Lewis acid from the anion moiety). By combining such non-reactive cation moiety with the anionic moiety, the Lewis acid generated from the anionic moiety can be efficiently used.

Moreover, as a cation part reactive with a Lewis acid, it shows a basicity, for example, the substituent which deactivates a catalytic capability by forming a salt with Lewis acid (for example, an amino group, an N-mono substituted amino group, an imino group (- And cation moieties having NH—). Therefore, the cation part which does not have group which can form a salt with Lewis acid is preferable.

Moreover, it is preferable that a cation part does not inhibit (well inhibits) generation | occurrence | production of Lewis acid from an anion part. Specifically, the cation part may be a cation part (structure) that does not generate protonic acid by light, and / or a cation part (structure) that does not decompose by light.

The center atom (cationic atom) of the cation moiety is not particularly limited and may be a sulfur atom (S), an iodine atom (I), or the like, but in particular a hetero atom selected from nitrogen, oxygen and phosphorus, in particular nitrogen and / Or oxygen may be used. The cation part which makes such a hetero atom the center atom often does not inhibit generation | occurrence | production of Lewis acid (for example, does not decompose by light), and it is easy to generate | occur | produce Lewis acid efficiently.

In the cation part which makes a hetero atom the center atom, the presence aspect of a hetero atom is not specifically limited, The atom which comprises a chain structure, and the atom which comprises a cyclic structure may be sufficient, Especially, a hetero ring (hetero ring) ) May be configured. That is, the cation part which makes such a hetero atom the center atom may be a heterocyclic ring or hetero ring (cation of) which makes at least 1 hetero atom selected from nitrogen, oxygen, and phosphorus the constituent atom of a ring. That is, the cation moiety preferably includes a hetero ring. If it is the said aspect, there exists a tendency for the characteristic as a polymerization initiator to improve.

Such a hetero ring may be either an aliphatic ring or an aromatic ring, but in particular, may be an aromatic ring (aromatic hetero ring).

Specific hetero rings include, for example, nitrogen-containing heterocycles [eg, monocyclic rings (pyridine rings (pyridinium rings), etc.), polycyclic rings (eg quinoline rings, isoquinoline rings, indole rings). Nitrogen-containing heterocycles (especially nitrogen-containing aromatic heterocycles), such as condensed rings such as bipyridinium rings), oxygen-containing heterocycles [for example, pyrilium rings (pyridinium rings), etc. And oxygen-containing aromatic heterocycles].

In addition, it is preferable that the hydrogen atom (protic hydrogen atom) is not substituted (bonded) to the hetero atom. For example, it is preferable that all the hydrogen atoms which comprise onium ion (for example, pyridinium (cation) etc.) are substituted by substituents other than a hydrogen atom.

As a substituent substituted (bonded) to such a hetero atom, the substituent etc. which were illustrated by the term of the said anion part are mentioned, for example. Representative substituents include, for example, hydrocarbon groups [for example, alkyl groups (eg, methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, etc.). A C _1-20 alkyl group, preferably a C _1-10 alkyl group, or the like, a cycloalkyl group (eg, a C _3-20 cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, preferably a C _4-8 cycloalkyl group) ), An aralkyl group (for example, a C _6-10 aryl C _1-4 alkyl group such as a benzyl group, a phenethyl group), an aryl group (for example, a C _6-10 aryl group such as a phenyl group) Hydrocarbon groups which may be present), etc. may be mentioned.

Moreover, in a cation part, the hetero ring may have a substituent. As a substituent substituted (bonded) to a hetero ring, it can select suitably according to the gap between HOMO-LUMO, etc., For example, the substituent illustrated by the term of the said anion part [For example, a hydrocarbon group (for example, A hydrocarbon group which may have a substituent such as an alkyl group, an aryl group), an acyl group (for example, a C _1-10 alkylcarbonyl group such as acetyl group; C _6-10 arylcarbonyl group (aroyl group) such as benzoyl group) Etc. can be mentioned. The substituent may be a substituted or unsubstituted hetero ring.

The substituents may be bonded to a hetero ring alone or in combination of two or more thereof.

Representative cationic moieties include, for example, nitrogen atom-containing heterocyclic skeletons [eg, N-substituted pyridinium skeletons, N-substituted bipyridinium skeletons, N-substituted quinolinium skeletons, N-substituted isoquinoli Cationic {eg, N-substituted pyridiniums [eg, N-substituted-arylpyridinium (eg, a skeleton having a substituent on a nitrogen atom of a nitrogen-containing heterocyclic ring as exemplified above) For example, N-substituted-C _6-10 arylpyridinium such as 4-phenyl-1-n-propylpyridinium, 4-phenyl-1-n-butylpyridinium, 4-phenyl-1-benzylpyridinium, and the like. Preferably N-alkyl-C _6-10 arylpyridinium and N-aralkyl-C _6-10 arylpyridinium, more preferably NC _1-20 alkyl-phenylpyridinium and NC _6-10 aryl C _1-4 Alkyl-phenylpyridinium), N-substituted-acylpyridinium (for example, N-substituted-C _6-10 arylcarbonylpyridinium such as 4-benzoyl-1-benzylpyridinium), and the like. Bipyridiniums [eg, N-values - bipyridinium (e.g., 1,1'-dioctyl-4,4'-bipyridinium such as N, N'- di-alkyl bipyridinium, preferably N, N'- di-C _{1- 20} alkylbipyridinium, more preferably N, N'-di C _1-10 alkylbipyridinium) and the like, N-substituted quinoliniums [eg, N-substituted-quinolinium (eg N-alkylquinolinium, such as 1-ethylquinolinium, preferably NC _1-20 alkyl-quinolinium; N-aralkylquinolinium such as 1-benzylquinolinium, preferably NC _{6 -10} aryl C _1-4 alkylquinolinium) and the like; N-substituted isoquinoliniums [eg, N-substituted-isoquinolinium (eg, 2-n-butylisoquinolinium and the like) N-alkylisoquinolinium, preferably NC _1-20 alkyl-isoquinolinium, N-aralkylisoquinolinium such as 2-benzylisoquinolinium, preferably NC _6-10 aryl C _1-4 alkyl quinolinyl titanium), etc.], etc.}, an oxygen atom-containing heterocyclic skeleton (e.g., containing the oxygen, such as the illustrated blood rilryum backbone Cation having a skeleton having a small ring) {e.g., piril ryumryu [e.g., alkyl rilryum blood (e.g., C _1-20 alkyl such as 2,4,6-trimethyl blood rilryum blood rilryum, preferably Preferably C _1-10 alkylpyryllium, more preferably C _1-4 alkylpyryllium), etc.], quaternary phosphoniums [for example, tetranaphthyl phosphonium, methyl trinaphthyl phosphonium, Phenacyl triphenyl phosphonium etc.] etc. are mentioned.

The cation moiety may preferably have a skeleton selected from an N-substituted pyridinium skeleton, an N-substituted bipyridinium skeleton, an N-substituted quinolinium skeleton, a quaternary phosphonium skeleton, and a pyryllium skeleton.

The compound of the present invention is a compound having an anion moiety and a cation moiety (or a compound in which an anion moiety and a cation moiety form a salt). The combination of the anion part and the cation part is not particularly limited as long as it can generate Lewis acid by light, and the combination of all of the anion part and the cation part is included.

The wavelength of the light capable of generating Lewis acid is not particularly limited and can be selected according to the use of the compound of the present invention and the like, but is, for example, 1000 nm or less (for example, 900 nm or less), preferably 800 nm or less ( For example, 750 nm or less), More preferably, it is about 650 nm or less (for example, 630 nm or less), 220 nm or more (for example, 230 nm or more), Preferably it is 240 nm or more (for example, For example, 245 nm or more), More preferably, it may be 250 nm or more (for example, 275 nm or more), More preferably, it may be 295 nm or more, and may be 240-700 nm normally.

The light which can generate | occur | produce Lewis acid may be light of the ultraviolet-ray-infrared region. Usually, although the light which can generate | occur | produce an acid has many lights of an ultraviolet-light region, even if it is the light of visible light-a near-infrared region, Lewis acid can be produced efficiently. Thus, although the compound of this invention can generate | occur | produce Lewis acid efficiently, under the shading | shielding or environment where light does not operate, decomposition | disassembly and generation | occurrence | production of a Lewis acid are highly suppressed, and it is excellent in stability or storage stability.

The compound of this invention can be manufactured by making an anion part and a cation part react. A usual method can be used for reaction (salt formation reaction). For example, salts of anion moieties (e.g., complex salts such as sodium salts, potassium salts, sodium / dimethoxyethane salts, etc.) and salts of cationic moieties (e.g. salts with halogens such as bromine) You may manufacture by making it react in a suitable solvent.

In addition, the anion part and the cation part can also be manufactured by the conventional method, and a commercial item may be used about the presence of a commercial item.

[Uses and Compositions of Compounds]

Since the compound of this invention generates Lewis acid by light (light energy), it can be said to be an optical Lewis acid generator. Such compounds (and photo Lewis acid generators) of the present invention can be used as various applications in which Lewis acids can be used, for example, as polymerization initiators (photo polymerization initiators, photo latent polymerization initiators), chemically amplified resist materials, and the like. Can be.

In particular, the compound (photo Lewis acid generator) of this invention can be used suitably as a photoinitiator (preferably a photocationic polymerization initiator). That is, the photoinitiator of this invention contains the compound of this invention.

The photoinitiator of this invention should just contain the compound of this invention, and may contain the other photoinitiator in the range which does not impair the effect of this invention. In a photoinitiator, the compound of this invention may be about 10-100 mass%, for example. The photoinitiator of this invention may contain the solvent and additive mentioned later.

Such a compound (photo Lewis acid generator) of this invention can comprise various compositions according to a use. That is, the composition of this invention contains the said compound (or agent), and the other component can be selected according to a use etc.

For example, when using the said compound as a polymerization initiator, the composition of this invention may contain the said compound and the polymeric compound which can superpose | polymerize with Lewis acid.

As such a polymeric compound, a cation polymeric compound [for example, cyclic ethers (epoxy compound, an oxetane type compound, etc.), vinyl ether, a nitrogen-containing monomer (for example, N -Vinylpyrrolidone, N-vinylcarbazole, etc.); In addition, an oligomer form may be sufficient as a polymeric compound.

You may use a polymeric compound individually or in combination of 2 or more types.

The polymerizable compound may typically include at least one selected from the cationic polymerizable compounds.

It does not specifically limit as an epoxy type compound (cationic polymerizable epoxy resin), For example, an aliphatic epoxy compound (for example, polyglycidyl ether of aliphatic polyols, such as hexanediol diglycidyl ether), alicyclic ring Family (alicyclic) epoxy compounds [eg, epoxycycloalkanes (eg, cyclohexene oxide, 3 ', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate)], aromatic epoxy Any of the compounds [for example, glycidyl ether of phenols (phenol, bisphenol A, phenol novolak, etc.)] may be sufficient, and these may be combined.

Among these, an alicyclic epoxy compound and an aromatic epoxy compound, especially an alicyclic epoxy compound may be used preferably.

In the epoxy compound, the epoxy group may be any of glycidyl ether type, glycidyl ester type, and olefin oxide (alicyclic) type.

In the composition, the ratio of the compound (or agent) is, for example, 0.001 to 20 parts by mass, preferably 0.01 to 10 parts by mass, and more preferably, relative to 100 parts by mass of the polymerizable compound. About 0.1-5 mass parts may be sufficient.

The composition is, if necessary, a solvent [for example, conventional solvents such as carbonates (for example, ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, diethyl carbonate, etc.)], additives (For example, a sensitizer, a pigment, a filler, an antistatic agent, a flame retardant, an antifoamer, a stabilizer, antioxidant, etc.) may be included.

You may use a solvent and an additive individually or in combination of 2 or more types.

When a composition contains a solvent, the ratio of solid content in a composition may be 0.01-50 mass%, for example, Preferably it is about 0.1-30 weight%.

In addition, the composition is, if necessary, an acid generator or a polymerization initiator not belonging to the category of the compound (photo Lewis acid generator) of the present invention [for example, a photoacid generator (a compound that generates protonic acid by light, Photoprotic acid generator)].

As mentioned above, the compound of this invention can form the composition which is comparatively stable and excellent stability. Therefore, this invention includes the storage method or manufacturing method of the said composition. In such a method, the composition may be usually stored or manufactured under light shielding or an environment in which light does not act.

More specifically, the present invention includes the following methods (A), (B) and the like.

(A) A method of preserving the composition (eg, a composition comprising at least the compound and the polymerizable compound) under shading.

(B) The method of manufacturing the said composition by mixing the said compound and another component (especially the composition containing at least a polymeric compound) under light shielding.

In the storage method, the storage period is not particularly limited, but may be, for example, 1 day or more, 3 days or more, 5 days or more, 10 days or more, 20 days or more, 30 days or more, or 50 days or more. The upper limit of the storage period is not particularly limited, but may be, for example, five years, four years, three years, two years, one year, six months, three months, or the like.

As light to light-shield, what is necessary is just to light-shield the light (light which has an absorption wavelength range with respect to the said compound) which the said compound produces Lewis acid. In light shielding, the degree of light shielding may be, for example, 20% or less, preferably 10% or less, more preferably 5% or less, particularly 3% or less, as the light transmittance of the wavelength or region. .

In the storage method and the production method, the temperature at the time of preservation or mixing is not particularly limited, and it is low temperature (for example, 10 ° C. or less), normal temperature (for example, 10 to 35 ° C.) or under heating ( For example, 35 degreeC or more) may be sufficient. In this invention, even if it is comparatively high temperature (for example, 20-80 degreeC, 25-70 degreeC, 30-60 degreeC, 35-50 degreeC, etc.), high stability can be implement | achieved.

The shading method is not particularly limited as long as it can be stored or mixed in a shading environment, and examples thereof include a method of storing or mixing in a dark place, a method of storing a composition in a shading container, a method of combining them, and the like. Can be.

As described above, the compound of the present invention generates Lewis acid by light. Therefore, this invention also includes the method of generating a Lewis acid by light irradiation (irradiating an active energy ray) to the said composition (the said compound or agent).

In such a method, when a composition contains a polymeric compound, superposition | polymerization of a polymeric compound advances with Lewis acid and the polymer of a polymeric compound can be manufactured. Therefore, this invention also includes the method of irradiating the said composition containing the polymeric compound which can superpose | polymerize with a Lewis acid, and manufacturing the polymer of a polymeric compound.

Moreover, depending on the kind of polymeric compound, a polymer forms hardened | cured material.

In light irradiation, if a Lewis acid can be generated as a light source, it will not specifically limit, For example, a fluorescent lamp, a mercury lamp (low pressure, medium pressure, high pressure, ultrahigh pressure etc.), a metal halide lamp, an LED lamp, a xenon lamp, carbon Arc lamps, lasers (for example, semiconductor solid lasers, argon lasers, He-Cd lasers, KrF excimer lasers, ArF excimer lasers, F2 lasers, etc.); In particular, in this invention, it is also possible to use the light source (LED lamp) of visible region.

Light irradiation time can be suitably selected according to the kind of compound, a polymeric compound, a light source, etc., and is not specifically limited.

The method may be carried out under heating. By carrying out under heating, the polymerization (curing) can be further realized with good efficiency.

As long as heating (heating process) can be performed with respect to the said composition or a compound, any of light irradiation, at the time of light irradiation (with light irradiation), after light irradiation may be sufficient, and you may carry out combining these. Typically, heating may be performed at the time of light irradiation and / or after light irradiation, and in particular, may be performed at least during light irradiation or during light irradiation.

Although it does not specifically limit as heating temperature, For example, 35 degreeC or more (for example, 35-150 degreeC), 40 degreeC or more (for example, 40-120 degreeC), 45 degreeC or more (for example, 45-100 degreeC) may be sufficient, and 50 degreeC or more (for example, 50-80 degreeC), 60 degreeC or more, 70 degreeC or more may be sufficient.

As a use of the composition of this invention, a coating material, a coating agent, various coating materials (hard coat, a pollution-resistant coating material, an antifogging coating material, a weatherproof coating material, an optical fiber, etc.), the backing agent of an adhesive tape, a peeling sheet for adhesive labels, for example (Coupling, peeling plastic film, peeling metal foil, etc.) peeling coating material, printing plate, dental material (dental compound, dental composite) ink, inkjet ink, electronic resist (circuit board, CSP, MEMS device, etc.) Manufacturing connection terminals, wiring pattern formation, etc.), resist films, liquid resists, negative resists (surface protective films such as semiconductor elements, interlayer insulating films, permanent film materials such as planarization films, etc.), MEMS resists, positive photosensitive materials, Negative photosensitive materials, various adhesives (temporary fixatives for various electronic components, HDD adhesives, adhesives for pickup lenses, functional films for FPD (deflection plates, anti-reflection films) ), Holographic resin, FPD material (color filter, black matrix, partition material, photospacer, rib, alignment film for liquid crystal, sealing compound for FPD), anisotropic conductive material, optical member, molding material (building Materials, optical components, lenses), casting materials, putty, glass fiber impregnating agent, filler material, sealing material, encapsulation material, optical semiconductor (LED) encapsulation material, optical waveguide material, nanoimprint material, light adjustment And micro-optical molding materials.

This invention is not limited to each embodiment mentioned above, A various change is possible and the embodiment obtained by combining suitably the technical means disclosed by each embodiment is also included in the technical scope of this invention.

Example

Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not restrict | limited by the following example originally, It is also possible to change suitably and to implement in the range which may be suitable for the meaning of the previous and the later. All of them are included in the technical scope of the present invention.

Synthesis Example 1 Preparation of Pentafluorophenylmagnesium Bromide

Magnesium (2.64 g, 0.109 mol) is added to the reaction vessel provided with a thermometer, a dropping funnel, a stirrer, a nitrogen gas inlet tube, and a reflux condenser, and after sufficiently substituted with nitrogen gas, dibutyl ether ( 52.3 g) was injected. In addition, normal butyl bromide (13.4 g, 0.098 mol) was injected into the dropping funnel.

Subsequently, the normal butyl bromide in dropping funnel was dripped at 30 degrees C or less, and the dibutyl ether solution of normal butyl magnesium bromide was obtained.

Separately, bromopentafluorobenzene (25.3 g, 0.103 mol) was injected into the dropping funnel. The dibutyl ether solution of pentafluorophenylmagnesium bromide was obtained by dripping the bromo pentafluorobenzene in the dripping funnel to the reaction liquid obtained by the said reaction at 30 degrees C or less.

It was confirmed that pentafluorophenylmagnesium bromide (the following compound) was obtained by F-NMR. Moreover, the conversion rate of bromopentafluorobenzene was 97% or more.

[Formula 3]

Synthesis Example 2 Preparation of Tris (pentafluorophenyl) borane

After completely replacing the inside of the reaction vessel as in Synthesis Example 1 with nitrogen gas, a boron trifluoride tetrahydrofuran complex (4.70 g, 0.034 mol) and methylcyclohexane (17.0 g) were injected into the reaction vessel as a boron compound. . In addition, a dibutyl ether solution containing pentafluorophenylmagnesium bromide obtained in Synthesis Example 1 was injected into the dropping funnel.

Subsequently, the dibutyl ether solution in the reaction container was dripped over 30 minutes at 30 degrees C or less, and then stirring was continued for 2 hours at room temperature. This obtained the dibutyl ether solution of tris (pentafluorophenyl) borane.

It was confirmed that tris (pentafluorophenyl) borane (the following compound) was obtained by F-NMR.

[Formula 4]

Synthesis Example 3 Preparation of Normal Butyl-tris (pentafluorophenyl) borate Sodium / Dimethoxyethane Complex

After sufficiently replacing the reaction vessel in Synthesis Example 1 with nitrogen gas, a dibutyl ether solution containing normal bromide magnesium bromide obtained by the same operation as in Synthesis Example 1 was injected into the reaction vessel. Moreover, the dibutyl ether solution containing the tris (pentafluorophenyl) borane obtained by the synthesis example 2 was injected into the dripping funnel.

Subsequently, the dibutyl ether solution in the dropping funnel was added dropwise over 15 minutes while stirring the dibutyl ether solution in the reaction vessel at 30 ° C. or lower, and then the reaction solution was heated to 50 ° C. and stirred for further 3 hours. This obtained normal butyl tris (pentafluorophenyl) borate magnesium bromide as a dibutyl ether solution.

After adding an excess amount of hydrochloric acid aqueous solution and stirring for 15 minutes, the reaction liquid was stopped still and the two-phase separated aqueous layer was taken out. Subsequently, an aqueous solution in which 1.20 g of sodium carbonate was dissolved in 18 g of water was added to the organic layer remaining in the reaction vessel, followed by stirring for 15 minutes. The reaction solution was then stopped and the aqueous phase separated in two phases was extracted and normal butyl-tris (penta) was added. It was set as the dibutyl ether solution of fluorophenyl) borate sodium salt.

Dimethoxyethane (4.56 g, 0.051 mol) was added to this dibutyl ether solution, and the crystal | crystallization of the normal butyl- tris (pentafluorophenyl) borate sodium / dimethoxyethane complex precipitated. This was filtered, washed with heptane, and air dried to obtain 11.8 g of a crystal of a normal butyl-tris (pentafluorophenyl) borate sodium / dimethoxyethane complex.

It was confirmed that normal butyl-tris (pentafluorophenyl) borate sodium / dimethoxyethane complex (following compound) was obtained by H-NMR and F-NMR.

[Formula 5]

Example 1 Preparation of 1,1'-diheptyl-4,4'-bipyridinium-normalbutyl-tris (pentafluorophenyl) borate

After fully replacing the inside of the reaction vessel in the same manner as in Synthesis Example 1 with nitrogen gas, the reaction vessel was then subjected to normal butyl-tris (pentafluorophenyl) borate sodium / dimethoxyethane (0.149 g, 0.17 m) obtained in Synthesis Example 3. Mol), ethyl acetate (3.9 g), and water (4.0 g) were injected. In addition, 1,1'-dioctyl-4,4'-bipyridinium bromide (0.089 g, 0.17 mmol) was weighed out and added to the reaction vessel.

It stirred at room temperature for 1 hour further. The reaction solution was left still to separate the two layers, and then the lower aqueous layer was removed. Further, water (5.0 g) was added to the organic layer, stirred and washed, and then stopped and the lower aqueous layer was removed, thereby obtaining 1,1'-diheptyl-4,4'-bipyridinium normal butyl-tris ( An ethyl acetate solution containing pentafluorophenyl) borate was obtained. Anhydrous magnesium carbonate was added to this solution, and it was dehydrated and dried. By removing the ethyl acetate with an evaporator, a solid (0.21 g) of 1,1'-diheptyl-4,4'-bipyridinium-normalbutyl-tris (pentafluorophenyl) borate was obtained.

It was confirmed that 1,1'-diheptyl-4,4'-bipyridinium normal butyl-tris (pentafluorophenyl) borate (the following compound) was obtained by H-NMR and F-NMR.

[Formula 6]

Synthesis Example 4 Preparation of ethyl-tris (pentafluorophenyl) borate sodium / dimethoxyethane complex

Ethyl magnesium bromide was obtained in the same manner as in Synthesis example 1 except that normal butyl bromide was changed to ethyl bromide.

Crystals of the ethyl-tris (pentafluorophenyl) borate sodium / dimethoxyethane complex were obtained by the same operation as in Synthesis Example 3, except that normal butylmagnesium bromide was changed to ethylmagnesium bromide obtained by the above reaction.

It was confirmed that ethyl-tris (pentafluorophenyl) borate sodium / dimethoxyethane complex (following compound) was obtained by H-NMR and F-NMR.

[Formula 7]

Synthesis Example 5 Preparation of benzyl-tris (pentafluorophenyl) borate sodium / dimethoxyethane complex

Benzyl magnesium bromide was obtained by the same operation as Synthesis Example 1 except that normal butyl bromide was changed to benzyl bromide.

Crystals of the benzyl-tris (pentafluorophenyl) borate sodium / dimethoxyethane complex were obtained by the same operation as in Synthesis Example 3, except that normal butylmagnesium bromide was changed to benzyl magnesium bromide obtained by the above reaction.

It was confirmed that benzyl-tris (pentafluorophenyl) borate sodium / dimethoxyethane complex (the following compound) was obtained by H-NMR and F-NMR.

[Formula 8]

Example 2 Preparation of 1,1'-Diheptyl-4,4'-bipyridinium Ethyl-tris (pentafluorophenyl) borate

By the same operation as in Example 1, except that the normal butyl-tris (pentafluorophenyl) borate sodium / dimethoxyethane complex was changed to the ethyl-tris (pentafluorophenyl) borate sodium / dimethoxyethane complex. Solid of 1,1'-diheptyl-4,4'-bipyridinium ethyl-tris (pentafluorophenyl) borate was obtained.

It was confirmed that 1,1'-diheptyl-4,4'-bipyridinium ethyl-tris (pentafluorophenyl) borate (the following compound) was obtained by H-NMR and F-NMR.

[Formula 9]

Example 3 Preparation of 1,1'-Diheptyl-4,4'-bipyridinium-benzyl-tris (pentafluorophenyl) borate

By the same operation as in Example 1, except that the normal butyl-tris (pentafluorophenyl) borate sodium / dimethoxyethane complex was changed to the benzyl-tris (pentafluorophenyl) borate sodium / dimethoxyethane complex, Solid of 1,1'-diheptyl-4,4'-bipyridinium benzyl-tris (pentafluorophenyl) borate was obtained.

It was confirmed that 1,1'-diheptyl-4,4'-bipyridinium benzyl-tris (pentafluorophenyl) borate (following compound) was obtained by H-NMR and F-NMR.

[Formula 10]

Example 4 Preparation of 4-phenyl-1-normalpropylpyridinium-benzyl-tris (pentafluorophenyl) borate

4-phenyl-1-normal by the same operation as in Example 3, except that 1,1'-diheptyl-4,4'-bipyridinium dibromide was changed to 4-phenyl-1-normalpropylpyridinium bromide. Solid of propylpyridinium benzyl-tris (pentafluorophenyl) borate was obtained.

It was confirmed that 4-phenyl-1-normalpropylpyridinium benzyl-tris (pentafluorophenyl) borate (the following compound) was obtained by H-NMR and F-NMR.

[Formula 11]

Example 5 Preparation of 4-benzoyl-1-benzylpyridinium-benzyl-tris (pentafluorophenyl) borate

4-benzoyl-1-benzylpyridinium by the same operation as in Example 1 using 4-benzoyl-1-benzylpyridinium bromide and benzyl-tris (pentafluorophenyl) borate sodium / dimethoxyethane complex Solid of benzyl-tris (pentafluorophenyl) borate was obtained.

It was confirmed that 4-benzoyl-1-benzylpyridinium benzyl-tris (pentafluorophenyl) borate (the following compound) was obtained by H-NMR and F-NMR.

[Formula 12]

Example 6 Preparation of 1-benzylquinolinium benzyl-tris (pentafluorophenyl) borate

1-benzylquinolinium benzyl-tris (penta) by the same operation as in Example 1 using 1-benzylquinolinium bromide and benzyl-tris (pentafluorophenyl) borate sodium / dimethoxyethane complex A viscous liquid of fluorophenyl) borate was obtained.

It was confirmed that 1-benzylquinolinium benzyl-tris (pentafluorophenyl) borate (following compound) was obtained by H-NMR and F-NMR.

[Formula 13]

Example 7 Preparation of 2,4,6-trimethylpyryllium benzyl-tris (pentafluorophenyl) borate

2,4,6-trimethylpyryllium by the same operation as in Example 1 using 2,4,6-trimethylpyryllium bromide and benzyl-tris (pentafluorophenyl) borate sodium / dimethoxyethane complex Solid of benzyl-tris (pentafluorophenyl) borate was obtained.

It was confirmed that 2,4,6-trimethylpyryllium benzyl-tris (pentafluorophenyl) borate (following compound) was obtained by H-NMR and F-NMR.

[Formula 14]

Synthesis Example 6 Preparation of Pentafluorophenylmagnesium Bromide

In the same manner as in Synthesis example 1, magnesium (2.48 g, 0.102 mol) was added to a reaction vessel equipped with a thermometer, a dropping funnel, a stirrer, a nitrogen gas inlet tube, and a reflux condenser, and after sufficiently substituted with nitrogen gas, the reaction vessel Cyclopentyl methyl ether (37.8 g) was injected into the flask.

Separately, bromopentafluorobenzene (21.0 g, 0.085 mol) was injected into the dropping funnel. About 30 g of bromopentafluorobenzene in the dripping funnel was dripped at 30 degreeC or less, and it stirred that for a while, it confirmed that reaction started by raising the temperature of the reaction liquid. Then, the remaining bromopentafluorobenzene was dripped at 30 degrees C or less, and the cyclopentyl methyl ether solution of pentafluorophenylmagnesium bromide was obtained.

It was confirmed that pentafluorophenylmagnesium bromide (the following compound) was obtained by F-NMR. Moreover, the conversion rate of bromopentafluorobenzene was 97% or more.

[Formula 15]

Synthesis Example 7 Preparation of Tris (pentafluorophenyl) borane

After sufficiently replacing the inside of the vessel with nitrogen gas using the same reaction vessel as in Synthesis Example 1, the cyclopentylmethylether solution of pentafluorophenylmagnesium bromide prepared in Synthesis Example 6 was transferred to the reaction vessel by passing through a glass filter. , Unreacted magnesium metal was removed. A boron trifluoride tetrahydrofuran complex (3.8 g, 0.0272 mol) was injected into the dropping funnel. Subsequently, after dripping over 30 minutes at 30 degrees C or less, stirring was continued for 2 hours at room temperature. This obtained the cyclopentyl methyl ether solution of tris (pentafluorophenyl) borane.

The same reaction vessel as in Synthesis example 1 was separately prepared, and isododecane (200 g) was injected into this. The cyclopentylmethylether solution of tris (pentafluorophenyl) borane obtained above was injected into the dropping funnel, and it was installed in the reaction container in which isododecane was injected. The solvent exchange of isododecane and cyclopentyl methyl ether was performed by dripping the cyclopentyl methyl ether solution of tris (pentafluorophenyl) borane under 70 degreeC under reduced pressure. Since magnesium salt which is a by-product precipitated in the reaction container, it was removed by filtration and the isododecane solution of tris (pentafluorophenyl) borane was obtained. Dibutyl ether (13.5 g) was added to prevent precipitation of tris (pentafluorophenyl) borane by lowering the liquid temperature.

It was confirmed that tris (pentafluorophenyl) borane (the following compound) was obtained by F-NMR.

[Formula 16]

Synthesis Example 8 Preparation of Normal Butyl Tris (Pentafluorophenyl) Borate and Sodium Aqueous Solution

After the inside of the vessel was sufficiently replaced with nitrogen gas using the same reaction vessel as in Synthesis Example 1, a dibutyl ether solution containing normal butylmagnesium bromide obtained by the same operation as in Synthesis Example 1 was injected. In addition, an isododecane solution containing tris (pentafluorophenyl) borane obtained in Synthesis Example 7 was injected into the dropping funnel.

Subsequently, the isodecane solution in the dropping funnel was added dropwise over 1 hour while the dibutyl ether solution in the reaction vessel was stirred at 30 ° C. or lower, and then the reaction solution was heated to 50 ° C. and stirred for 1 hour, further 70 ° C. The temperature was raised to and stirred for 2 hours. This obtained the reaction liquid of normal butyl tris (pentafluorophenyl) borate magnesium bromide.

After adding an excess amount of hydrochloric acid aqueous solution and stirring for 15 minutes, the reaction liquid was stopped still and the aqueous phase separated by two phases was taken out. Subsequently, an aqueous solution in which sodium carbonate (2.7 g, 0.026 mol) was dissolved in 18.0 g of water was added to the organic layer remaining in the reaction vessel, followed by stirring for 15 minutes. The reaction solution was then stopped and the aqueous phase separated in two phases was taken out. It was set as the isododecane solution of butyl-tris (pentafluorophenyl) borate sodium salt.

Water (160 g) was added to this isododecane solution, and an organic solvent was distilled off together with water under reduced pressure to obtain an aqueous solution of normal butyl-tris (pentafluorophenyl) borate sodium salt (84.0 g, borate solid content 14.7). mass%).

It confirmed that the normal butyl- tris (pentafluorophenyl) borate sodium solution was obtained by H-NMR and F-NMR.

[Formula 17]

Synthesis Example 9 Preparation of benzyl-tris (pentafluorophenyl) borate and sodium aqueous solution

Benzyl magnesium bromide was obtained by the same operation as Synthesis Example 1 except that normal butyl bromide was changed to benzyl bromide.

An aqueous solution of benzyl-tris (pentafluorophenyl) borate and sodium salt was obtained by the same operation as in Synthesis Example 8 except that normal butylmagnesium bromide was changed to benzyl magnesium bromide obtained by the above reaction.

It was confirmed that benzyl-tris (pentafluorophenyl) borate and sodium aqueous solution were obtained by H-NMR and F-NMR.

[Formula 18]

Example 8 Preparation of 4-phenyl-1-normalbutylpyridinium normalbutyl-tris (pentafluorophenyl) borate

4-phenyl-1-normal-butylpyridinium bromide (0.125 g, 0.42 mmol) was injected into the branch flask equipped with the stirrer, and water (0.56 g) was added to make an aqueous solution. The normal butyl-tris (pentafluorophenyl) borate aqueous sodium solution (1.70 g, borate solid content 14.7 mass%) obtained by the synthesis example 8 was dripped under 0 degreeC, stirring.

Stirring was continued as it was for 1 hour, and it heated up at 50 degreeC further, and stirred for 1 hour. A white solid precipitated during the dropping. The solid was filtered, washed with a small amount of water, and dried to give a white solid (0.31 g) of 4-phenyl-1-normalbutylpyridinium normalbutyl-tris (pentafluorophenyl) borate.

It was confirmed that 4-phenyl-1-normal butylpyridinium normal butyl-tris (pentafluorophenyl) borate (following compound) was obtained by H-NMR and F-NMR.

[Formula 19]

Example 9 Preparation of 4-phenyl-1-normalbutylpyridinium benzyl-tris (pentafluorophenyl) borate

4-phenyl-1-normalpropyl was produced in the same manner as in Example 8 except that the aqueous normal butyl-tris (pentafluorophenyl) borate solution was changed to the aqueous benzyl-tris (pentafluorophenyl) borate solution. Solid of pyridinium benzyl-tris (pentafluorophenyl) borate was obtained.

It was confirmed that 4-phenyl-1-normalpropylpyridinium benzyl-tris (pentafluorophenyl) borate (the following compound) was obtained by H-NMR and F-NMR.

[Formula 20]

Example 10 Preparation of 1-ethylquinolinium benzyl-tris (pentafluorophenyl) borate

Normal butyl-tris (pentafluorophenyl) borate aqueous sodium solution to benzyl-tris (pentafluorophenyl) borate aqueous sodium solution, 4-phenyl-1-normal butylpyridinium bromide to 1-ethylquinolinium bromide Except having changed, the solid of 1-ethylquinolinium benzyl- tris (pentafluorophenyl) borate was obtained by operation similar to Example 8.

It was confirmed that 1-ethylquinolinium benzyl-tris (pentafluorophenyl) borate (the following compound) was obtained by H-NMR and F-NMR.

[Formula 21]

Example 11 Preparation of 2-benzylisoquinolinium benzyl-tris (pentafluorophenyl) borate

Normal butyl-tris (pentafluorophenyl) borate and sodium aqueous solution is benzyl-tris (pentafluorophenyl) borate and sodium aqueous solution and 4-phenyl-1-normal butylpyridinium bromide is 2-benzyl isoquinolinium bromide A solid of 2-benzylisoquinolinium benzyl-tris (pentafluorophenyl) borate was obtained by the same operation as in Example 8 except for changing to.

It was confirmed that 2-benzylisoquinolinium benzyl-tris (pentafluorophenyl) borate (following compound) was obtained by H-NMR and F-NMR.

[Formula 22]

[Comparative Example 1] Production of tetraphenylphosphonium benzyl-tris (pentafluorophenyl) borate

Tetraphenylphosphonium benzyl-tris (pentafluorophenyl) by the same operation as in Example 1 using tetraphenylphosphonium bromide and benzyl-tris (pentafluorophenyl) borate sodium / dimethoxyethane complex A viscous viscous liquid was obtained.

It was confirmed that tetraphenylphosphonium benzyl-tris (pentafluorophenyl) borate (the following compound) was obtained by H-NMR and F-NMR.

[Formula 23]

[Comparative Example 2] Preparation of tetranormalbutylammonium benzyl-tris (pentafluorophenyl) borate

Tetranormalybutylammonium benzyl-tris (pentafluorophenyl) by the same operation as in Example 1 using tetranormalbutylammonium bromide and benzyl-tris (pentafluorophenyl) borate sodium / dimethoxyethane complex A viscous viscous liquid was obtained.

It was confirmed that tetranormalbutylammonium benzyl-tris (pentafluorophenyl) borate (the following compound) was obtained by H-NMR and F-NMR.

[Formula 24]

Comparative Example 3 Preparation of 1-normal-butylpyridinium-benzyl-tris (pentafluorophenyl) borate

1-Normalbutylpyridinium benzyl-tris (penta) by the same operation as in Example 4 using 1-normal butylpyridinium bromide and benzyl-tris (pentafluorophenyl) borate sodium / dimethoxyethane complex A viscous liquid of fluorophenyl) borate was obtained.

It was confirmed that 1-normal butylpyridinium benzyl-tris (pentafluorophenyl) borate (the following compound) was obtained by H-NMR and F-NMR.

[Formula 25]

[Confirmation of the presence or absence of Lewis acid]

Confirmation test of the presence or absence of Lewis acid generation was done using the compound obtained by the Example and the comparative example.

That is, 1 mass part of compounds obtained by the Example and the comparative example were melt | dissolved in 1 mass part of propylene carbonate. The obtained solution (15 mg) was irradiated with UV light for 5 minutes at 25 degreeC using the high pressure mercury lamp (irradiation intensity of 365 nm wavelength; 50 mW / cm <2>).

F-NMR analysis of the solution after light irradiation confirmed the production of tris (pentafluorophenyl) borane which is a Lewis acid.

[Polymerization Evaluation Experiment]

The polymerization test was conducted using the compound obtained by the Example and the comparative example.

That is, 1 mass part of compounds obtained by the Example and the comparative example were melt | dissolved in 1 mass part of propylene carbonate. 1 mass part of the said mixed solution was mixed with 99 mass parts of polymeric compounds [alicyclic epoxy resin (Celoxide 2021P, the Daicel company make) or aromatic epoxy resin (bisphenol A diglycidyl ether, the Tokyo Chemical Co., Ltd. make).

In addition, the alicyclic epoxy resin was used for the compound obtained in Examples 1-7 and Comparative Examples 1-3, and both the alicyclic epoxy resin and aromatic epoxy resin were used for the compound obtained in Examples 8-11, respectively.

The obtained solution (5 mg) was irradiated with UV light for 5 minutes (irradiation intensity of 365 nm wavelength; 20 Hz / cm 2) using a high pressure mercury lamp at 25 ° C. (not heated), 50 ° C. or 80 ° C. The amount of polymerization calorific value at that time was measured by photo-DSC. The start point and the end point of light irradiation were connected linearly with respect to the peak of the polymerization calorific value, and the obtained area was taken as the calorific value.

In addition, about the compound obtained in Examples 1-7 and Comparative Examples 1-3, it implemented only at 50 degreeC.

[Calculation Method of HOMO-LUMO Gap of Cation Part]

HOMO and LUMO energies of the compounds obtained in Examples and Comparative Examples were calculated using Gaussian09, software for calculating molecular orbits, manufactured by Gaussian, USA.

As the calculation method, the density range function method B3LYP was selected, and the basis function was 6-311 G (d, p). The structural optimization of the target molecular structure was performed, and the energy levels (eV unit conversion value) of HOMO and LUMO after structural optimization were computed.

The results are shown in Tables 1, 2, 3 and 4 together with the structures of the compounds.

As is clear from the results of the above table, in the compound of the example, Lewis acid was generated by light. And the polymerization advanced satisfactorily by using the compound of the example.

[1 liquid stability evaluation test]

Using the compound obtained in the Example and cumene-4-yl (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate (henceforth iodonium borate salt) which is a typical photo-acid generator as a comparison, it is 1 Liquid stability evaluation test was done.

1 mass part of the compound obtained in Example 8, the compound obtained in Example 9, or iodonium borate salt was melt | dissolved in 1 mass part of propylene carbonate, and the mixed solution was obtained.

1 part by mass of the mixed solution was mixed with 99 parts of an alicyclic epoxy resin (Celoxide 2021P, manufactured by Daicel Co., Ltd.), sealed, and stored at 40 ° C under light shielding.

1 liquid stability was evaluated by viscosity measurement. The value compared with the viscosity when days were passed was made into the initial viscosity (0 days of elapsed days) as a reference | standard (thickened multiple 1), and it was set as the thickening multiple (viscosity at the time of measurement / initial viscosity).

The results are shown in the following table.

As is clear from the results of the above table, the compounds obtained in Examples 8 and 9 had a high one-liquid stability, and the increase in viscosity of the resin composition was suppressed.

Thus, it turned out that the compound obtained by the Example is highly suppressed in generation | occurrence | production of Lewis acid under light shielding, and has the outstanding stability.

(Example 12)

Viscosity of quinolinium benzyl-tris (pentafluorophenyl) borate in the same manner as in Example 6 except that quinolinium bromide was used instead of 1-benzylquinolinium bromide in Example 6 A liquid was obtained.

It was confirmed that quinolinium benzyl-tris (pentafluorophenyl) borate (the following compound) was obtained by H-NMR and F-NMR.

[Formula 26]

About the obtained compound, when the presence or absence of generation | occurrence | production of Lewis acid was confirmed by the same method as the above, it confirmed that Lewis acid was generated.

Moreover, in the obtained compound, HOMO-LUMO Gap of the cation part was calculated by the same method as the above, and it was 4.287 eV.

Industrial availability

According to the compound of the present invention, Lewis acid can be generated by light. Therefore, the compound of this invention can be applied to various uses using a Lewis acid, for example, a polymerization initiator, a resist, etc.

Claims (13)

A compound having an anion moiety having an aryl group containing boron as a center atom and containing at least one halogen atom and a cation moiety, wherein the compound can generate Lewis acid from the anion moiety by light irradiation. The method of claim 1,
The compound whose anion part is represented by following formula (1).

(In the formula, Ar ¹ , Ar ² and Ar ³ are an aryl group which may have the same or different substituents, and R ¹ represents a substituent.) The method of claim 2,
In the formula (1), at least one of Ar ¹ , Ar ² and Ar ³ is an aryl group having at least one halogen atom, and R ¹ is a hydrocarbon group or a hydroxyl group which may have a substituent. The method according to any one of claims 1 to 3,
The compound in which the cation moiety consists of cation whose gap between HOMO-LUMO is 5.3 eV or less. The method according to any one of claims 1 to 4,
Compounds in which the cation moiety is unreactive to Lewis acids. The method according to any one of claims 1 to 5,
A compound in which the cation moiety does not generate protonic acid by light. The method according to any one of claims 1 to 6,
A compound in which the cation moiety is a cation having a hetero atom selected from nitrogen, oxygen, and phosphorus as a central atom. The method according to any one of claims 1 to 7,
The compound whose wavelength of light is 240 nm or more. The photoinitiator containing the compound as described in any one of Claims 1-8. A composition comprising the compound or agent according to any one of claims 1 to 9. Furthermore, the method of irradiating the composition of Claim 10 containing the polymeric compound which can superpose | polymerize with Lewis acid to manufacture the polymer of a polymeric compound. The method of claim 11,
Manufacturing method produced under heating. The method of storing the composition of Claim 10 under light shielding.